KR20190022325A - Adhesive resin composition and laminate - Google Patents

Abstract

The present invention provides an adhesive resin composition, which can be uniformly coated and has high adhesive properties and acid-resistant strength, and a laminate using the adhesive resin composition. According to the present invention, the adhesive resin composition comprises: an acid-modified polyolefin resin component (A) having a melting point of more than 80°C to 140°C or less; a crosslinking agent component (B); and a solvent component (S). The solvent component (S) contains an aromatic solvent (S1), an aliphatic solvent (S2) and a ketone-based solvent (S3), wherein the aromatic solvent (S1) has the highest boiling point. When a total amount of the solvent component (S) is 100 parts by mass, the solvent component (S) contains 50 to 80 parts by mass or less of the aromatic solvent (S1), 10 to 30 parts by mass or less of the aliphatic solvent (S2) and 5 to 20 parts by mass or less of the ketone-based solvent (S3).

Description

[0001] ADHESIVE RESIN COMPOSITION AND LAMINATE [0002]

The present invention relates to an adhesive resin composition and a laminate.

BACKGROUND ART In the field of an outer body and a package used for the exterior use and packaging of industrial products such as electronic devices and batteries and daily necessities such as foods, beverages, cosmetics and medicines, resin materials such as polyethylene and polypropylene, And a metal material are stacked in combination.

Various studies have been made on an adhesive composition for bonding the resin material and the metal material in order to improve the adhesion thereof.

For example, in Patent Document 1, a resin (C) obtained by graft-polymerizing an acid-modified polyolefin resin (A) and a polyamide resin (B) as an adhesive resin composition of a melt- (A), the polyamide resin (B) and the epoxy group-containing resin (A), and the graft copolymer (G) obtained by further graft polymerizing the epoxy group- D) is 100% by mass, the amount of the acid-modified polyolefin resin (A) is 85 to 98% by mass, the amount of the polyamide resin (B) is 1 to 9% By mass to 14% by mass of the adhesive resin composition.

Japanese Patent No. 5771493

The adhesive resin composition as disclosed in Patent Document 1 has a low solubility because it contains an olefin resin component having a high melting point and is hardly used as a solvent-based adhesive resin composition. In addition, when a solvent-based adhesive resin composition is produced, it is difficult to uniformly coat a crosslinking agent component in the coating process.

Incidentally, it is assumed that the adhesive resin composition used in the battery outer body such as a lithium secondary battery, a hydrogen fuel cell, or a solar cell is in contact with an electrolytic solution which is acidic. For this reason, the adhesive resin composition is required to have high acid resistance in addition to high adhesiveness. In the present specification, " high acid resistance strength " means that the bonding strength is not lowered even when contacted with an acid.

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and it is an object of the present invention to provide an adhesive resin composition which can be uniformly coated, has high adhesiveness, and further has high acid resistance, and a laminate using the same.

That is, the present invention employs the following configuration.

[1] An adhesive resin composition comprising an acid-modified polyolefin resin component (A) having a melting point of more than 80 캜 and not more than 140 캜, a crosslinking agent component (B), and a solvent component (S) (S1), an aliphatic solvent (S2) and a ketone solvent (S3), wherein the aromatic solvent (S1) has the highest boiling point and the total amount of the solvent component (S) is 100 parts by mass , At least 50 parts by mass and not more than 80 parts by mass of the aromatic solvent (S1), 10 parts by mass or more and 30 parts by mass or less of the aliphatic solvent (S2), 5 parts by mass or more of the ketone solvent (S3) By mass or less.

[2] The adhesive resin composition according to [1], further comprising a resin component (C) having an amino group at the molecular end.

[3] The adhesive resin composition according to [1] or [2], wherein the aliphatic solvent (S2) is methylcyclohexane.

[4] The adhesive resin composition according to any one of [1] to [3], wherein the ketone-based solvent (S3) is methyl ethyl ketone.

[5] The adhesive resin composition according to any one of [1] to [4], wherein the aromatic solvent (S1) is toluene.

[6] The adhesive resin composition according to any one of [1] to [5], wherein the solid content concentration is 5 mass% or more and 20 mass% or less.

[7] The adhesive resin composition according to any one of [1] to [6], wherein the acid addition amount of the acid-modified polyolefin resin component (A) is 0.5% by mass or more and 3.0% by mass or less.

[8] The adhesive resin composition according to any one of [1] to [7], wherein the crosslinking component (B) is a resin component (B1) having an epoxy group in the molecule.

[9] The resin composition according to any one of [1] to [2], wherein the resin component (C) is at least one member selected from the group consisting of an olefin resin in which the molecular end is modified with an amino group, a polyamine resin, a polyamide resin in which the molecular ends are modified with amino groups, a melamine resin, ] The adhesive resin composition according to any one of [1] to [8].

[10] The adhesive resin composition according to any one of [2] to [9], wherein the resin component (C) has a weight average molecular weight of 2000 or more.

[11] The adhesive resin composition according to any one of [1] to [10], wherein the cross-linking agent component (B) is a novolak-modified epoxy resin.

[12] The adhesive resin composition according to any one of [1] to [11], wherein the cross-linking agent component (B) contains a compound having a bisphenol A structure in the molecule.

[13] The adhesive resin composition according to any one of [1] to [12], further comprising an isocyanate compound (D).

[14] A laminate having an adherend and an adhesive resin layer laminated on one side of the adherend, wherein the adhesive resin layer is formed from the adhesive resin composition according to any one of [1] to [13].

According to the present invention, it is possible to provide an adhesive resin composition which can be uniformly coated, has high adhesiveness, and further has high acid resistance, and a laminate using the same.

Fig. 1 is a schematic view of a device used in the peeling test.
Fig. 2 is a schematic view for explaining the lamination state of the test pieces used in the peeling test.

In the present specification, as the molecular weight of the polymer, a weight average molecular weight in terms of polystyrene by GPC (Gel Permeation Chromatography) is used.

 Hereinafter, the present invention will be described based on preferred embodiments.

<Adhesive Resin Composition>

The adhesive resin composition of the present invention comprises an acid-modified polyolefin resin component (A) having a melting point of more than 80 캜 and not more than 140 캜, a crosslinking agent component (B), and a solvent component (S). The solvent component (S) further contains an aromatic solvent (S1), an aliphatic solvent (S2) and a ketone solvent (S3). Wherein the aromatic solvent S1 has the highest boiling point and the total amount of the solvent component S is 100 parts by mass, the amount of the aromatic solvent S1 is 50 parts by mass or more and 80 parts by mass or less, S2) of 10 parts by mass or more and 30 parts by mass or less, and the ketone solvent (S3) of 5 parts by mass or more and 20 parts by mass or less. The adhesive resin composition of the present invention is in a liquid phase. For this reason, an adhesive film can be formed by applying to an adherend and drying.

The adhesive resin composition of the present invention has an effect of uniformly coating and high acid resistance in addition to high adhesiveness. Therefore, it can be suitably used in a battery external body such as a lithium secondary battery, a hydrogen fuel cell, a solar cell, etc. in which contact with an acidic electrolytic solution is assumed.

Hereinafter, each component constituting the adhesive resin composition of the present invention will be described.

Component (A)

The adhesive resin composition of this embodiment contains an acid-modified polyolefin resin component (hereinafter referred to as &quot; component (A) &quot;) having a melting point of more than 80 캜 and 140 캜 or lower.

In the present embodiment, heat resistance can be imparted to the adhesive resin composition by using the component (A) having a high melting point and having a melting point exceeding 80 캜. The melting point is preferably 85 DEG C or higher, more preferably 90 DEG C or higher, and particularly preferably 95 DEG C or higher.

In the present embodiment, the component (A) is a polyolefin resin modified with an unsaturated carboxylic acid or a derivative thereof and has an acid functional group such as a carboxyl group or a carboxylic anhydride group in the polyolefin resin. Since the acid functional group such as a carboxyl group or a carboxylic anhydride group interacts with the surface of the adherend, component (A) contributes to adhesion.

The component (A) is obtained by modifying a polyolefin resin with an unsaturated carboxylic acid or a derivative thereof, or copolymerizing an olefin with an acid functional group-containing monomer. Among them, as the component (A), a material obtained by acid-modifying a polyolefin-based resin is preferable. Examples of the acid modification method include graft modification in which a polyolefin resin and an acid functional group-containing monomer are melt-kneaded in the presence of a radical polymerization initiator such as an organic peroxide or an aliphatic azo compound.

Examples of the polyolefin-based resin include polyethylene, polypropylene, poly-1-butene, polyisobutylene, copolymers of propylene and ethylene, and copolymers of propylene and olefin-based monomers.

Examples of the olefin-based monomer in the case of copolymerization include 1-butene, isobutylene, 1-hexene and the like.

Among them, the component (A) is preferably a maleic anhydride-modified polypropylene from the viewpoints of adhesiveness, durability and the like. ·

Weight average molecular weight

In the present embodiment, the weight average molecular weight of the component (A) is preferably 30,000 or more, more preferably 40,000 or more, and particularly preferably 50,000 or more. It is preferably 150,000 or less, more preferably 140,000 or less, and particularly preferably 130,000 or less. The upper limit value and the lower limit value may be arbitrarily combined.

ㆍ acidity

Examples of the unsaturated carboxylic acid used for the modification include acrylic acid, methacrylic acid, maleic acid, nadic acid, fumaric acid, itaconic acid, crotonic acid, citraconic acid, sorbic acid, mesaconic acid, have. Examples of the derivative include acid anhydrides, esters, amides, imides and metal salts. Specific examples thereof include maleic anhydride, itaconic anhydride, citraconic anhydride, nadic acid anhydride, methyl methacrylate Maleic acid monoethyl ester, acrylamide, maleic acid amoamide, maleimide, N-butyl maleimide, sodium acrylate, sodium methacrylate, and the like. Of these, unsaturated dicarboxylic acids and derivatives thereof are preferable, and maleic anhydride or phthalic anhydride is particularly preferable.

In the present embodiment, it is preferable that the carboxylic acid addition amount of the component (A) is 0.5% by mass or more and 3.0% by mass or less.

&Quot; Crosslinking agent component (B) &quot;

The adhesive resin composition of the present embodiment contains a crosslinking agent component (B) (hereinafter referred to as &quot; component (B) &quot;).

Examples of the component (B) include a copolymer of an epoxy group-containing vinyl monomer, a phenoxy resin synthesized from bisphenols and epichlorohydrin, and various epoxy resins. In the present embodiment, it is preferable that the crosslinking agent component (B) is a resin component (B1) having an epoxy group in the molecule.

Examples of the component (B) include glycidyl esters such as glycidyl methacrylate (GMA) and glycidyl acrylate, glycidyl ethers such as allyl glycidyl ether, epoxy alkenes such as epoxy butene May be used.

In the copolymer of an epoxy group-containing vinyl monomer, other monomers copolymerizable with the epoxy group-containing vinyl monomer include olefins such as ethylene and propylene, acrylic monomers such as (meth) acrylate, and vinyl acetate.

Examples of the copolymer of an epoxy group-containing vinyl monomer include ethylene-glycidyl methacrylate (E-GMA) copolymer.

As the phenoxy resin, those having an epoxy group at both ends are used, and examples of the bisphenols include bisphenol A, bisphenol F, and copolymerization type thereof.

Examples of the component (B) include a bisphenol-type epoxy resin, a novolak-type epoxy resin, a glycidylamine-type epoxy resin, and a glycidyl ester-type epoxy resin. In the present embodiment, the component (B) is preferably a novolak-modified epoxy resin. In the present embodiment, it is preferable that the component (B) contains a compound having a bisphenol A structure in the molecule.

From the viewpoint of improving the adhesiveness, the component (B) preferably has a weight average molecular weight (Mw) in the range of 500 to 50,000.

ㆍ Content

In the present embodiment, the content of the resin component (B) relative to 100 parts by mass of the acid-modified polyolefin resin component (A) is 1 part by mass or more, preferably 5 parts by mass or more, and more preferably 10 parts by mass or more . It is preferably 30 parts by mass or less, more preferably 25 parts by mass or less, and most preferably 22 parts by mass or less.

The upper limit value and the lower limit value may be arbitrarily combined. By setting the content within the above range, an adhesive resin composition having high adhesiveness and high durability can be obtained.

&Lt; Component (C) &gt;

The adhesive resin composition of the present embodiment preferably contains a resin component having an amino group at the molecular end (hereinafter referred to as &quot; component (C) &quot;). The component (C) generates an amine when it is attacked by, for example, hydrofluoric acid contained in the electrolytic solution. The generated amine neutralizes hydrofluoric acid and can exhibit high acid resistance. For this reason, component (C) contributes to acid resistance.

(C) is preferably at least one member selected from the group consisting of an olefin resin in which the molecular end is modified with an amino group, a polyamine resin, a polyamide resin in which the molecular end is modified with an amino group, a melamine resin and a urea resin.

More specifically, as the component (C), diethylene triamine (DETA), triethylenetetramine (TETA), tetraethylenepentamine (TEPA), amine-modified hydrogenated styrenic thermoplastic elastomer in which the terminal of the molecule is modified with an amino group, polyethyleneimine, Nylon 6, nylon 66, nylon 12, and the like.

In the present embodiment, the weight average molecular weight of the component (C) is preferably 2000 or more, more preferably 5000 or more, from the viewpoint of improving the crosslinking strength at the time of bonding. The upper limit value is not particularly limited, but may be, for example, 1000000 or less, 500000 or less, or 200000 or less.

ㆍ Content

The content of the resin component (C) is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, more preferably 5 parts by mass or more, and more preferably 6 parts by mass or more, per 100 parts by mass of the acid- modified polyolefin resin component (A) Is particularly preferable. The amount is preferably 15 parts by mass or less, more preferably 14 parts by mass or less, more preferably 13 parts by mass or less, particularly preferably 12 parts by mass or less. By the addition amount as described above, the bonding strength can be sufficiently maintained while maintaining a high neutralization effect on hydrofluoric acid.

The upper limit value and the lower limit value may be arbitrarily combined.

&Quot; Solvent component (S) &quot;

The solvent component (S) may be an aromatic solvent (S1) (hereinafter also referred to as "component (S1)"), an aliphatic solvent (S2) Based solvent S3 (hereinafter, also referred to as &quot; component (S3) &quot;). Among them, the component (S1) has the highest boiling point.

ㆍ aromatic solvent (S1)

Examples of the component (S1) include toluene (boiling point: 110.6 ° C), ortho-xylene (boiling point: 144 ° C), meta-xylene have. In the present embodiment, the component (S1) is preferably toluene.

Aliphatic solvent (S2)

(Boiling point: 101 占 폚), heptane (boiling point: 98.42 占 폚), and octane (boiling point: 125 占 폚). In the present embodiment, the component (S2) is preferably methylcyclohexane.

Ketone type solvent (S3)

Examples of the component (S3) include acetone (boiling point: 56 ° C), methyl ethyl ketone (boiling point: 79.64 ° C), methyl isobutyl ketone (boiling point: 116.2 ° C), and cyclopentanone (boiling point: 49 ° C). In the present embodiment, methyl ethyl ketone is preferable as the component (S3).

The combination of the components (S1), (S2) and (S3) is not particularly limited so long as the solvent component (S) is a combination in which the boiling point of the component (S1) As a preferable example, it is preferable to select toluene as the component (S1), select methylcyclohexane as the component (S2), and select methylethylketone as the component (S3). Further, in the present embodiment, it is more preferable that the solvent component (S) is composed of only these three kinds.

In the present embodiment, the content of the components (S1), (S2) and (S3) is preferably 50 parts by mass or more and 80 parts by mass or less , The component (S2) is 10 parts by mass or more and 30 parts by mass or less, and the component (S3) is 5 parts by mass or more and 10 parts by mass or less.

The component (S1) exhibits a certain solubility in both the components (A) and (B). The component (S2) has a low solubility in the component (B), but exhibits a high solubility in the component (A). The component (S3) has a low solubility in the component (A), but exhibits a high solubility in the component (B).

In the present embodiment, by combining solvent components exhibiting high solubility with respect to each resin component, the solubility of the resin component is improved, and the adhesive resin composition can be uniformly coated. The adhesive resin composition of the present embodiment is excellent in both of the components (A) and (B) when the adhesive resin composition is applied to the adherend, even if the components (S2) And the component (S1) having a high boiling point remains. Therefore, it is presumed that coagulation of the resin component and occurrence of lumps can be suppressed and uniform coating can be performed.

«Optional ingredients»

The adhesive resin composition of the present embodiment preferably contains an isocyanate compound (D) (hereinafter referred to as &quot; component (D) &quot;).

Examples of the component (D) include bifunctional or trifunctional isocyanate compounds, bifunctional or trifunctional or higher functional epoxy compounds, bifunctional or trifunctional or higher functional acrylate compounds, metal chelate compounds, and silane coupling agents, carbodiimide Compounds and the like. Among them, a polyisocyanate compound (bifunctional or trifunctional or higher isocyanate compound) is preferable, and a trifunctional or higher isocyanate compound is more preferable.

(D), it is preferably contained in an amount of 0.1 part by mass or more and 10 parts by mass or less based on 100 parts by mass of the component (A). The component (D) may be used alone or in combination of two or more.

The isocyanate compound having three or more functional groups may be a polyisocyanate compound having at least three isocyanate (NCO) groups in one molecule. Examples of the polyisocyanate compound include aliphatic isocyanates, aromatic isocyanates, non-cyclic isocyanates, and alicyclic isocyanates. Specific examples of the polyisocyanate compound include aliphatic isocyanate compounds such as hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI) and trimethylhexamethylene diisocyanate (TMDI), diphenylmethane diisocyanate (MDI) Aromatic isocyanate compounds such as rylene diisocyanate (XDI), hydrogenated xylylene diisocyanate (H6XDI), dimethyl diphenylene diisocyanate (TOID), and tolylene diisocyanate (TDI).

Examples of the isocyanate compound having three or more functional groups include biuret-modified or isocyanurate-modified products of diisocyanates (compounds having two NCO groups in one molecule), trimethylolpropane (TMP), and tri- or more polyols such as glycerin (A compound having at least three OH groups) and the like (polyol modified product).

The adhesive resin composition of the present embodiment preferably has a solid content concentration of 3% by mass or more, more preferably 5% by mass or more, and particularly preferably 7% by mass or more. Further, it is preferably 20 mass% or less, more preferably 18 mass% or less, and particularly preferably 16 mass% or less. The upper limit value and the lower limit value of the solid concentration can be arbitrarily combined. By making the solid concentration as described above, an adhesive resin composition having good wettability and good applicability can be obtained.

<Laminate>

The laminate of the present invention is formed by laminating an adhesive resin layer made of the adhesive resin composition of the present invention on at least one side of a substrate. The adhesive resin layer is formed on one side or both sides of the substrate so that it can be adhered to the adherend using the adhesive resin layer. The substrate is not necessarily required to have adhesiveness to the substrate itself, and it is preferable that the substrate is adherable to the adhesive resin layer. Metal, glass, plastic, and the like. In the present embodiment, the adhesive resin composition is coated on an adherend and dried to form an adhesive resin layer.

Example

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

<Acid resistance test>

The acid resistance test will be described with reference to Fig.

First, the laminate shown in Fig. 2 was used as a test piece.

The adhesive resin composition layer 30 of each of the examples and the comparative examples was applied to a polyethylene terephthalate film 32 having a thickness (L ₆ ) of 100 μm, a length (L ₄ ) of 50 mm and a width (L ₅ ) L ₇ ) × 10 mm (L ₈ ) × 3 μm (L ₉ ), and dried at 110 ° C. for 1 minute to form an adhesive film on the polyethylene terephthalate film.

Thereafter, a polypropylene film 31 having a thickness (L ₃ ) of 50 μm, a length (L ₁ ) of 50 mm and a width (L ₂ ) of 10 mm was applied to the adhesive film forming side by applying a load of 2 kg at 130 ° C , Respectively. At this time, as shown in Fig. 2, one end was aligned and laminated.

This laminate was immersed in a water tank 37 of an acidic solution (reference numeral 36) having a pH of 2 containing 1000 ppm of hydrogen fluoride for 1000 hours so that the polypropylene film 31 was stretched in the adhesive resin layer 30, the polyethylene terephthalate film 32 and the polypropylene film 31 were respectively bent. The polyethylene terephthalate film 32 is gripped and fixed by the crushing strip 34 to form the polypropylene film 31 in the water tank as indicated by reference numeral 35. The polypropylene film 31, Tensile and peel strengths were measured in the tensile direction.

The tensile speed was measured at 50 mm / min. The peel strength (N / mm &lt; 2 &gt;) at this time was measured and evaluated according to the following evaluation criteria.

[Evaluation standard]

The evaluation was carried out in the following four stages, and the results were evaluated as acceptable.

?: 0.5 N / mm 2 or more

?: 0.3 N / mm 2 or more and less than 0.5 N / mm 2

?: 0.1 N / mm2 or more and 0.3 N / mm2 or less

×: less than 0.1 N / mm 2

&Lt; Adhesion test &gt;

The same laminate as the test piece used in the &quot; acid resistance test &quot;

The resulting laminate was placed in a high-temperature thermostat at 80 DEG C and a humidity of 95% for 1000 hours.

Thereafter, it was dried for 1 hour under conditions of 23 캜 and a humidity of 50%.

The polyethylene terephthalate film and the polypropylene film were respectively bent at the end portions of the adhesive layer so that the polypropylene film was on the tensile side. The polypropylene film was gripped with a gripper, and the polyethylene terephthalate film was gripped with a gripper and fixed, and the tensile and peel strengths of the polypropylene film were measured.

The tensile speed was measured at 50 mm / min. The peel strength (N / mm &lt; 2 &gt;) at this time was measured and evaluated according to the following evaluation criteria.

[Evaluation standard]

The evaluation was carried out in the following four stages, and the results were evaluated as acceptable.

?: 0.7 N / mm 2 or more

?: 0.5 N / mm 2 or more and less than 0.7 N / mm 2

?: 0.3 N / mm 2 or more and less than 0.5 N / mm 2

×: less than 0.3 N / mm 2

<Uniform Coating Test>

The obtained adhesive resin composition was coated on a PET film by hand coating and dried at 100 DEG C for 1 minute to prepare a sample having a size of 20 cm x 30 cm to confirm visually whether or not there was a coating stain. &Lt; / RTI &gt; The evaluation was carried out in the following four stages, and the results were evaluated as acceptable.

A: No coating unevenness.

○: There is fine coating unevenness.

?: The resin component and the solvent component are separated.

X: The resin component is precipitated.

<Heat resistance test>

The same laminate as the test piece used in the &quot; acid resistance test &quot;

The obtained laminate was placed in a high-temperature thermostat at 120 캜 for 1000 hours.

Thereafter, the laminate was taken out, and the state of the laminate was observed, and the peeling was visually observed. The results are shown in the following table.

Evaluation was carried out according to the following criteria. The evaluation was carried out in the following four stages, and the results were evaluated as acceptable.

◎: Good peeling without visible peeling.

○: No noticeable peeling was observed with eyes.

△: There was some peeling off.

X: Peeling was observed on the whole surface.

&Lt; Preparation of adhesive resin composition &gt;

(A), the components (B), (C), (S) and (D) shown in Tables 1 and 2 were mixed, A composition was obtained. In the following Tables 1 and 2, numerical values shown in brackets indicate blending amounts (parts by mass).

In the table, each symbol means the following materials.

(A) -1: maleic acid-modified polypropylene-1, molecular weight: 90000, acid part: 1.1% by mass, melting point: 90 ° C

(A) -2: maleic acid-modified polypropylene-2, molecular weight: 70000, acid part: 1.5% by mass, melting point: 80 占 폚

(B) -1: Epoxy A, special novolak type epoxy resin (epoxy equivalent 200, softening point 70 캜), bisphenol A skeleton in the molecule, and epoxy group of novolac structure.

(C) -1: amine-modified hydrogenated styrenic thermoplastic elastomer

(C) -2: Nylon resin (having an amino group as a terminal substituent)

(D) -1: Isocyanate compound (tolylene diisocyanate)

(S) -1: Toluene (boiling point 110.6 ° C)

(S) -2: methylcyclohexane (boiling point: 101 DEG C)

(S) -3: methyl ethyl ketone (boiling point: 79.64 ° C)

As shown in the above results, the adhesive resin compositions of Examples 1 to 7 containing the component (S) including the solvent (S1), the solvent (S2) and the solvent (S3) can be uniformly coated, Respectively.

On the other hand, in Comparative Examples 1 to 3 and 7 in which only the solvent S1 was used, the solubility of the resin component was insufficient, and the coating could not be uniformly applied. In addition, even if the solvent (S1), the solvent (S2) and the solvent (S3) were contained, the solubility of the resin component was insufficient, I could not. In Comparative Example 6 using the component (A) having a melting point of 80 占 폚, the heat resistance was poor.

In addition, the adhesive property of Example 6 was higher than that of the other examples, and the adhesive property was excellent.

The present invention relates to an adhesive resin composition layer, and more particularly, to an adhesive resin composition layer comprising an adhesive resin composition layer 30, an adhesive resin composition layer 31, a polypropylene film 32, a polyethylene terephthalate film 33, 34,

Claims (14)

An adhesive resin composition comprising an acid-modified polyolefin resin component (A) having a melting point of more than 80 캜 and not more than 140 캜, a crosslinking agent component (B), and a solvent component (S)
Wherein the solvent component (S) contains an aromatic solvent (S1), an aliphatic solvent (S2) and a ketone solvent (S3), wherein the aromatic solvent (S1) has the highest boiling point, (S 3) is not less than 50 parts by mass and not more than 80 parts by mass, the aliphatic solvent (S 2) is not less than 10 parts by mass and not more than 30 parts by mass, and the ketone solvent (S 3) Is not less than 5 parts by mass and not more than 20 parts by mass. The method according to claim 1,
And a resin component (C) having an amino group at a molecular end. 3. The method according to claim 1 or 2,
Wherein the aliphatic solvent (S2) is methylcyclohexane. 4. The method according to any one of claims 1 to 3,
Wherein the ketone-based solvent (S3) is methyl ethyl ketone. 5. The method according to any one of claims 1 to 4,
Wherein the aromatic solvent (S1) is toluene. 6. The method according to any one of claims 1 to 5,
Wherein the solid content concentration is 5 mass% or more and 20 mass% or less. 7. The method according to any one of claims 1 to 6,
Wherein the acid addition amount of the acid-modified polyolefin resin component (A) is 0.5% by mass or more and 3.0% by mass or less. 8. The method according to any one of claims 1 to 7,
Wherein the crosslinking agent component (B) is a resin component (B1) having an epoxy group in the molecule. 9. The method according to any one of claims 2 to 8,
Wherein the resin component (C) is at least one member selected from the group consisting of an olefin resin in which the molecular end is modified with an amino group, a polyamine resin, a polyamide resin in which the molecular end is modified with an amino group, a melamine resin and a urea resin. 10. The method according to any one of claims 2 to 9,
Wherein the resin component (C) has a weight average molecular weight of 2000 or more. 11. The method according to any one of claims 1 to 10,
Wherein the cross-linking agent component (B) is a novolak-modified epoxy resin. 12. The method according to any one of claims 1 to 11,
Wherein the crosslinking component (B) contains a compound having a bisphenol A structure in the molecule. 13. The method according to any one of claims 1 to 12,
And an isocyanate compound (D). An adhesive resin composition comprising an adherend and an adhesive resin layer laminated on one side of the adherend, wherein the adhesive resin layer is formed from the adhesive resin composition of any one of claims 1 to 13.

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